Azo dyestuffs and process of making same



Patented Sept. 2 1, 1926.

7 UNITED STATES PATENT OFFICE.

AX ISLER AND LUKAS voN MECHEL, OF BASEL, SWITZERLAND, ASSIGNORS Tosocurry OF CHEMICAL INDUSTRY IN BASL'E, or BASEL, SWITZERLAND.

A ZO DYESTI J'FFS AND PROCESS Oi MAKING SAME.

No Drawing. Application filed December 9 .1924, Serial No. 754,841, andin Switzerland December 28, 1923.

The invention relates to the new dyestufis, the process of making same,as well as to the material dyed with the new dyestuff. It has been foundthat new azo dyestuffs corresponding to the general formula:

iii which R stands for any aromatic residue, may be obtained by coupling3-hydroxynaphthalene-1: 8-dicarboxylic acid with a .diazo compound. Thecoupling component ticularly appropriate.

imparts to the dyestuffs quite a. general mordant character, which canbe enhanced by selection of the diazo compound used. For that purposediazo compounds derived from O-hydroxyamino compounds are par- The newdyestufl's form red to violet, blue, and black powders, dissolving inwater to yellow-red, red, violet and blue solutions, in concentratedsulfuric acid to red, violet and blue solutions, and in aqueous sodiumcarbonate solutions, to yellow-red and blue solutions, and dyeing theanimal and vegetable fibre from yelloworange to red, Violet, blue, blackand brown tints which, when afterchromed, yield fast orange to red,blue, green-black and brownblack tints. Their chrome printing on cottonyields orange to violet blue, grey and brown to black tints.

These dyestuffs, when treated .-with re, ducing'agents, split into anaromatic amino compound and the 4-amino-3-hydroxynaphv thalene-l8-dic'arboxylic acid.

The following examples illustrate the invention without limiting it, theparts being by weight:. I

Ewample 1.

9.3 parts of aniline are .dia zntized as usual and the solution thusobtained is introduced.

wards brown when afterchromed. The formula of the new dyestufi' is mostprobably noo 00H Example 2. 23.3 parts of 1-hydroxy-2-aminobenzene-4-sulpho-6-carboxylic acid are diazotized as usual and introducedinto asolution of 21.4 parts of 3-hydroxynaphthalene-1:8-

S Oi

OOH

HOQ 0011 Eapample 3.

23.5 parts of 3-hydroxy-naphthalene-1:8-

dicarboxylic acid are introduced into 54:

parts of-caustic soda solution of 30 per cent. strength; the whole iscooled and there are added 31.7 parts ofthe sodium salt of the nitrateddiazo-compound from 1-amino-2- hydroxynaphthalene 4 sulphonic a c i (1.

After stirring. for some time the temperature is allowed to risegradually to 15 C. and stirring is continued at this temperature untilthe diazo-compound has disappeared.

Dilution with water follows and the dye- I stufl is separated-byacidification- Itis a,

blackish powder and dissolves in water to violet tints which become darkgreen and a red-violet solution, in dilute caustic soda fast whena-fterchromed.

solution to a violet-brown solution and in concentrated sulphuric acidto a blue solu- The following table indicates the main properties of anumber of dyestufi's obtain- 5 tion. It dyes Wool in an acid bathblackable by this invention 10 Solution in Solution in 1 Component to be3 5: 25 Solution in aqueous concentrated Dyeing on gggt zg aggit gg3:53:32 dmzomed powder. $32 55 gg wool chromed. coppered. on cotton.

Aniline Red Yellow-red Yellow-red Red. Yellow-red Yellow-brownParanitraniline Yellow-red Violet-red Blue-rem.-. Brown.. Brown Brown.Meta-anhino-ben- Brown Yell0W-red Brownred-- Yellow-red Orange OrangeOrange.

1010 aci Anthranilic acid"- Red Yellow-red Yellow-red Blue-rcd. RedViolet-brown. Red-brown. b-nitro-fi-amino- Orange-yel- Yellow-redBrown-red Blue-red. Yellow-orange Brown l-benzoic acid. low. 75-sulpho-3-amino- Brown-red... Yellow-red Brown-red.- Blue-red Orange.Brown l-benzoic acid. 4-(ihllorofi-amino- Brown Blue-red-.. BluevioleL.Violet-blue" Bordeaux. Dark-blue Violet-grey. Steel-blue.

-p eno. p 4-nilt1ro-2l-amino-1- Black Violet Violet Blue-redViolet-brown Black Black-brown p eno. 4:6i-digitro -2-amino-Brown-black- Violet-red-.- Bordeaux." Blue-red Violet-black"Reddish-black Grey-black- -p eno 5-nihtro-g-amino-l- Brown Blue BlueBlue-red Violet-brown. Green-black Blue-grey.

p eno 4-methyl-6nitro-2- Black Blue Blue Violet-red--. Brown-grey-.Blue'greynn Blue-grey.

amino-l-phenol. z-amling-l-pheugl-l- Brown-black. Brown-red- Blue-redBordeaux"..- Red-blue... Violet Violet.

su p onic aci 4-methyl-2-amin0- Violet-black. Blue Blue-red Bordeaux..Grey-bluc Blue-violeL. R eddish- -1- henol -6-sulblue.

p onic 801d: 4-chloro-2-amino-l- Brown-black. Blue Reddis'h- Red-violet.Violetbrown- Blue Violet-blue.- Blue.

p h e n 0 l-6-sulblue. I I phonic acid. 6-nitro-2-amin 0- Black VioletViolet Blue-red.. Blue- Vi l Blue-black.

l-p h e n o l-4-sulphonic acid. 4-nitro-2-amino- Brown Violet Red-violetBlue-red--- I Black Greenisli-v Violet-black.

1- henol-G-sulblack.

13 chic acid. 2-amino- 1 phe- Brown Red Violet Blue-rein. Bordeaux Darkviolet Red-violet.-- Violet.

nol-4-sulpho-6- carboxylic acid. 2-amino-.1- phe- Dark brown.. RedViolet Violet-blue. Bordcaux Blue-violet... Brown-vio- Violet.

nol-4-chloro-6 let. carboxylic acid. 2- arlnirioltphg- Grey-black...Blue-violet" Red-violet, Blue-red--. Bordcaux Violet-brown. Brown-violetViolet.

no Ill lO- car oxylic acid. 2':1min0-i-phenol- Redi s h Blue-red-.Vi0let Blue-redo Brown- Black-brown. .Violet. 4 c:.rboxylic.lcid. brown.6-uitro-2-amino; Brown-black. Bordeaux.-- Bordeaux-" Bluc-rcd-Black-brown. Violet-black" Violet-black.

1 phenol 4 carooiylic acid. l-amino-l-phenol- Red-brown Yellow-redBrown-rcd Blue-red. Orange-brown Violet-brown- Yellow- Brown.

G-carboxylic acid. brown. Nitrated diazo-com- I g on Bligzishpow-Red-violet" Blue Blue Black-violet, Dark green naphthalene 4 sulphonicacid.

001m. of the Solution in aque- Solution in concen Component to-bediazotized. Stuff powder Solution in water. ous sodium cartratedsulphuric Dyeing on cotton.

. bonate. acid.

Bnzidine.-- Brown- Bordeaux Bordeaux Toluidine.-- Brownl Red-violetViolet Blue :Dimiisirlinn Brown. Red-blue Violet-blue What we claim islene-l 8-dicarboxylic acid with a diazo-com- 1. As a 'new process theherein descrlbed pound. manufacture of new azo .dyestufls corre- 2. As anew process the hereln described sponding to the general formula:manufacture of the new azo dyestufls corresponding to the generalformula:

J" v a R 0H 1 H00 OOH wherein R stands'for any aromatic residue,consisting in coupling 3-hydroxynaptha- OOH wherein stands for a residueof a diazov wherein R stands which dyestuffs form and blue solutions,'and vegetable fibre violet, blue, 7 I when afterchromed,

'and which dyestufi's yield, when cotton with tized aromaticortho-hydroxyamino compound, consisting in couplingS-hydroxynapthalene-l:8-dicarboxylic acid with a dlazotized aromaticortho-hydroxyamino compound. 7 v

3. As a new process the herein described manufacture of new azodyestuffs corresponding to the general formula N=NR H00 OOH for aresidue of a diazotized ortho-amino-phenol compound, consisting incoupling 3-hydroxynaphthalene- 1 8-dicarboxylic crtho-amino-phenolcompound.

, 4. As new products the herein described I new azo dyestuffscorresponding to the general formula:

H00 oon' wherein R stands for any aromatic residue, red to vlolet, blueand black powders, dissolving in water to yellow-red, red, blue andviolet solutions, in concentrated sulphuric acid to yellow-red, violetand greenish-blue solutions, in aqueous sodium carbonate solutions toyellow-red yellow-orange to red, black and brown tints which, yield fastorange to and brown-black tints, printed on chrome mordants, orange toviolet, blue grey, black and brown tints, (1 when treated with reducinginto an aromatic amino compound and 4- red, blue, green-blackamino-3-hydroxy-naphthalene-1 8-dicarbox 'ylic acid. v

1 5, As new products the herein described new azo dyestuffs eralformula:

no 00E wherein 3 acid with a diazotized tions, in aqueous and dyeing.the animal.

agents split stuffs of claim 4.

of claim 5.

corresponding to the gen-- tized ortho-hydroxy-amino compound, whichdyestuffs form brown and black powders, dissolving in water toyellow-red, violet and blue solutions, in concentrated sulphuric acid tored, violet and blue solutions, in aqueous sodium carbonate solution toBordeaux, violet and blue solutions, dyeing wool Bordeaux, violet, blue,black and brown tints which, when afterchromed, ield fast violet,- blue,green, black and rown tints when printed on cotton with chrome mordantsyield violet to grey, blue and blackish tints, and which dyestuffs,

when treated with reducing agents split into an ortho-hydroxy-aminocompound and 4- amino-3-hydroxynaphthalene-1 :8-dicarboxylic acid. 7

6. As new products the herein described new azo dyestuffs correspondingto the gen eral formula:

N=NR ortho-amino-phenol compound and -amino- 3-hydroxynaphthalene-1S-dicarboxylic acid. 7. The material dyed with the new dye- 8. Thematerial 9. The mar a dyed withithe new dyestuffs of claim 6.

'ey, blue and dyed the dyestu ifs 'In witness whereof we have hereunto'gned our names this 25th day of Novem- MAXISLER- 4 LUKAS v, MECHEL.

stands m: a residue .of adiazo-

